Dicyclopentamethylenethiuram Disulfide as Precursor of Mononuclear Complexes: Oxidative Cleavage of Metal-Metal Bond in [CpMo(CO)3]2 and Molecular Structure of cis-[CpMo(CO)2{S2C-N(CH2)5}]
The reaction of [CpMo(CO)3]2 with dicyclopentamethylenethiuram disulfide in refluxing xylene resulted a novel mono nuclear complex,
cis-[(CpMo(CO)2{S2C-N(CH2)5}] as red crystals in moderate yield. The compound was formed by the oxidative cleavage of metal-metal bond in [CpMo(CO)3]2 together with a reductive sulfur-sulfur bond scission in the ligand.
References
[1]
Amdio, E., Cavinato, G., Domella, A., Ronchini, L., Toniolo, L. and Vavasori, A. (2009) New Carboalkoxybis(Triphenylphosphine)Palladium(II) Cationic Complexes: Synthesis, Characterization, Reactivity and Role in the Catalytic Hydrocarboalkoxylation of Ethene. X-Ray Structure of Trans-[Pd(COOMe)(TsO)(PPh3)2]·2CHCl3. Journal of Molecular Catalysis A: Chemical, 298,103.
https://doi.org/10.1016/j.molcata.2008.10.002
[2]
European Food Safety Authority (EFSA) (2011) The European Union Report on Pesticide Residues. EFSA, 9, 2430.
[3]
Rehman, M., Hussain, A., Rehman, Z., Rauf, F.A., Hassan, A., Tahir, A. and Ali, S. (2010) New Tetrahedral, Square-Pyramidal, Trigonal-Bipyramidal and Octahedral Organotin(IV) 4-Ethoxycarbonylpiperazine-1-Carbodithioates: Synthesis, Structural Properties and Biological Applications. Journal of Organometallic Chemistry, 695, 1526. https://doi.org/10.1016/j.jorganchem.2010.03.008
[4]
Brown Jr., T.L., Lemayand, E.H. and Bursten, B.E. (2000) Chemistry: The Central Science. 8th Edition, Prentice Hall International, Washington.
[5]
Doadrio, A.L., Sotelo, J. and Fern’andez-Ruano, A. (2002) Synthesis and Characterization of Oxovanadium(IV) Dithiocarbamates with Pyridine. Quimica Nova, 25, 525. https://doi.org/10.1590/S0100-40422002000400002
[6]
Sharma, M. and Sachar, R. (2009) Synthesis and Characterization of the Adducts of bis(N,N-Diethyldithiocarbamato)Oxovanadium(IV) with Substituted Pyridines. Oriental Journal of Chemistry, 25, 215.
[7]
Manohar, A., Ramalingam, K., Bocelli, G. and Cantoni, A. (2010) Synthesis, Spectral and Single Crystal X-Ray Structural Studies on bis(2,2'-bipyridine)Sulphidom(II) (M = Cu or Zn) and Diaqua 2,2'-Bipyridine Zinc(II)Sulphatedihydrate. Journal of the Serbian Chemical Society, 75, 1085. https://doi.org/10.2298/JSC091019097M
[8]
Ekennia, A.C. (2013) Antibacterial Application of Novel Mixed-Ligand Dithiocarbamate Complexes of Nickel (II). Journal of Applied Chemistry, 5, 36.
[9]
Geetha, N. and Thirumaran, S. (2008) Characterization Studies and Cyclic Voltammetry on Nickel(II) Amino Acid Dithiocarbamates with Triphenylphosphine in the Coordination Sphere. Journal of the Serbian Chemical Society, 73, 169.
https://doi.org/10.2298/JSC0802169G
[10]
Sovilj, S.P., Vuckovic, G., Leovac, M. and Minic, D. (2000) Dinuclear Copper(II) Complexes of N,N',N\",N\"'-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane and Some N,S or N,O Bidentate Ligands. Polish Journal of Chemistry, 74, 945.
[11]
Sharma, M., Sharma, A. and Sachar, R. (2013) Preparation and Characterization of the Adducts of bis(N,N-diethyldithiocarbamato)oxovanadium(IV) and copper(II) with n-propylamine and Isopropylamine. Chemical Science Transactions, 2, 367.
https://doi.org/10.7598/cst2013.265
[12]
Sharma, M., Sharma, A. and Sachar, R. (2012) Synthesis and Characterization of the Adducts of Morpholinedithioccarbamate Complexes of Oxovanadium(IV), Nickel(II) and Copper(II) with Piperidine and Morpholine. Journal of Chemistry, 9, 1929. https://doi.org/10.1155/2012/689501
[13]
Onwudiwe, D.C. and Ajibade, P.A. (2011) Synthesis, Characterization and Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of N-methyl-N-phenyl Dithiocarbamate: The Single Crystal Structure of [(C(6)H(5))(CH(3))NCS(2)](4)Hg(2). International Journal of Molecular Sciences, 12, 1964.
https://doi.org/10.3390/ijms12031964
[14]
Osowole, A.A., Kolawole, G.A. and Fagade, O.E. (2005) Synthesis, Physicochemical, and Biological Properties of Nickel(II), Copper(II), and Zinc(II) Complexes of an Unsymmetrical Tetradentate Schiff Base and Their Adducts. Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 35, 829.
https://doi.org/10.1080/15533170500358168
[15]
Kolawole, G.A. and Osowole, A.A. (2009) Synthesis and Characterization of Some metal(II) Complexes of Isomeric Unsymmetrical Schiff Bases and Their Adducts with Triphenylphosphine. Journal of Coordination Chemistry, 62, 1437.
https://doi.org/10.1080/00958970802621512
Shashi, B.K., Geetanjli, K. and Priyanka (2011) Synthesis and Characterization of Pyridine Adducts of Some Transition Metal 4-Methylpiperazine-1-Carbodithioic Acid Complexes. Himachal Pradesh University Journal, 1.
[18]
Mamba, S.M. (2011) Synthesis, Characterization and Application of Dithiocarbamate Transition Metal Complexes. PhD Thesis, University of Johannesburg, Johannesburg.
[19]
Karlin, K.D. (2005) Progress in Inorganic Chemistry. John Wiley and Sons, Inc., 53, 71.
[20]
Deeming, A.J., Forth, C. and Hogarth, G. (2007) Synthesis and Crystal Structure of [Ru8(μ5-S)2(μ4-S)(μ3-S)(μ-CNMe2)2(μ-CO)(CO)15] Formed via the Double Sulphur-Carbon Bond Cleavage of dithiocarbamate ligands. Journal of Organometallic Chemistry, 692, 4000. https://doi.org/10.1016/j.jorganchem.2007.05.044
[21]
Karim, M.M., Abser, M.N., Hassan, M.R., Ghosh, N., Alt, H.G., Richards, I. and Hogarth, G. (2012) Oxidative-Addition of Thiuram Disulfides to Osmium(0): Synthesis of cis-[Os(CO)2(S2CNR2)2] (R = Me, Et, Cy, CH2CH2OMe) and Molecular Structures of cis-[Os(CO)2(S2CNMe2)2] and [(MeOCH2CH2)2NCS]2. Polyhedron, 42, 84. https://doi.org/10.1016/j.poly.2012.04.042
[22]
Ziegler, M.L., Weber, H., Nuber, B. and Serhadle, O. (1987) Synthesis and Characterization of the Zwitterion S2CC(NMe2)2, a Transition Metal Induced Carbon-Carbon Coupling. Complex Chemistry of the Zwitterions S2CC(NR2)2. Zeitschrift für Naturforschung, 42b, 141.
[23]
Catheline, D., Roman, E. and Astruc, D. (1984) Reactivity of the Monodentdithiocarbamate Ligand in CpFe(CO)2(η1-S2CNR2). Inorganic Chemistry, 23, 4508.
https://doi.org/10.1021/ic00194a021
[24]
Maheu, L.J., Miessler, G.L., Berry, J., Burow, M. and Pignolet, L.H. (1983) Di- and Tri-thiocarbamato Complexes of Osmium(III) and the Crystal and Molecular Structure of [Os2(SeS2CNMe2)2(S2CNMe2)3]PF6. Inorganic Chemistry, 22, 405.
https://doi.org/10.1021/ic00145a009
[25]
Hope, J.M., Martin, R.L., Taylor, D. and White, A.H. (1977) Ring Expansion in a Metal-Dithiocarbamate Complex by Oxygen Insertion; Synthesis and Properties of [Cr(S2CNR2)2(OS2CNR2)]. The X-Ray Structure of bis[NN-diethyl (dithiocarbamato-SS’)][NN-diethyl(dithioperoxycarbamato-OS)]chromium(III). Journal of the Chemical Society, Chemical Communications, 99.
https://doi.org/10.1039/C39770000099
[26]
Martin, R.L., Patrick, J.M., Skelton, B.W., Taylor, D. and White, A.H. (1982) Crystal Structure of bis[N,N-diethyl(dithiocarbamato-S,S’)]-[N,N-diethyl(dithioperoxycarbamato-O,S)]chromium(III). A Redetermination. Australian Journal of Chemistry, 35, 2551. https://doi.org/10.1071/CH9822551
[27]
Fackler, J.P. and Holah, D.G. (1966) Sulfur Chelates. II. Five-Coordinate Transition Metal Complexes. Inorganic and Nuclear Chemistry Letters, 2, 251.
https://doi.org/10.1016/0020-1650(66)80055-7
[28]
Pignolet, L.H., Lewis, R.A. and Holm, R.H. (1971) Synthesis and Stereochemical Rearrangements of Complexes Containing the Fe-S6 Core. Journal of the American Chemical Society, 93, 360. https://doi.org/10.1021/ja00731a011
[29]
Shi, Y., Cheng, G., Lu, S., Guo, H., Wu, Q., Huang, X. and Hu, N. (1993) The Cleavage Reaction of the Molybdenum-Molybdenum Triple Bond. The Crystal Structures of Molybdenum Complexes [CpMo(CO)2(C5H4NS)], [CpMo(CO)2 (C9H6NS)]O:PPh3 and [CpMo(CO)2(S2CNMe2)]. Journal of Organometallic Chemistry, 455, 115. https://doi.org/10.1016/0022-328X(93)80389-S
[30]
To a xylene (40 mL) of [CpMo(CO)3]2 (0.200 g, 0.408 mmol) Was Added Dicyclopentamethylenethiuram Disulfide (0.196 g, 0.612mmol) and the Reaction Mixture Was Refluxed for 1 Hour. The Color Was Changed from Red to Red Brown. The Solvent Was Removed under Reduced Pressure and Residue Chromatographed by TLC on Silica. Elution with Cyclohexane/Dichloromethane (3:2 V/V) Gave One Band cis-[(CpMo(CO)2{S2C-N(CH2)5}] (0.167 g, 36.16%) as Red Brown Crystal from Dichloromethane/Hexane Mixture at ?4 oC. Elemental Analysis: Found C = 41.36, H = 3.99, N = 3.70, S = 16.94% and C13H15MoNO2S2 Requires C = 41.34, H = 3.98, N = 3.71, S = 16.96%. IR (υCO) in cm?1: 1857.53(s), 1949.15(s). 1H NMR (ppm): 1.54 (m, 3H), 1.63 (m, 3H), 3.56 (m, 2H), 3.79 (m, 2H), 5.41 (s, 5H). FAB mass (m/z):377 [M+], 349 [M+-CO], 321 [M+-2CO], 257 [M+-2CO-2S], etc.
[31]
Crystal Data for cis-[(CpMo(CO)2{S2C-N(CH2)5}]: Empirical Formula C13H15MoNO2S2, MW = 377.32, Triclinic, Space groupP1, a = 6.449(7) A, b = 10.634(10) A, c = 11.383(12) A, α = 71.94(3)°, β = 82.31(3)°,γ = 76.43(3)°, V =719.9(13) A3, T= 273(2) K, Z= 2, μ=1.197 mm-1, F(000) 380, density (calculated) 1.741 Mg/m3, 7722 Reflections Collected, 3303 Independentreflections [R(int) = 0.0477]. The Final R1 = 0.0486, wR2 = 0.1288 [I > 2σ (I)], R Indices (all data) R1 = 0.0719, wR2 = 0.1566.
[32]
Lide, D.R. (2003-2004) Handbook of Chemistry and Physics. 84th Edition, CRC Press, Sec. 9, 10.
